Composition of matter and method of making same



Patented Mc aieis I} 2,375,531

f UNITED 'ISTATES PATENT OFFICE COMPOSITION OF MA no mo METHOD OF MAKING, SAME Melvin De Groote, University City, Bernhard Keiser, Webster Groves, and Arthur F. Wirtei, Kirkwood, Mo., assignors to Petrolito Corporation, Ltd., Wilmington, DeL, a corporation of Delaware No Drawing. Application June 21, 1943,

' Serial No. 491,133

4 Claims. (01. coo-405i This invention relates to a new composition vided the oxidation is sufllciently prolonged to of matter, our present application being a con- 1 obtain the desired drastic oxidation. Usually, tinuation-in-part of our pending applicatio the time required is at least about 8 to 10 hours Serial No. 440,751, filed April 27, 1942. under conditions most favorable to oxidation, 1. e., One object of our invention'is to provide a new 5 blowing at a relatively high temperature, and for chemical product or compound that is particulars certain fatty compounds much more prolonged y adaptedfor use as a demulsifler in the resoluoxidation, 1. e.,- Several ay even Weeks, is tion of crude oil emulsions. desirable, especially under conditions less favor- Another object of our invention is to provide a able to rapid oxidatio n a y event. Whether practicable method for manufacturing said new in the oxidation is Producd y Continued mild chemical product or compound. r dation, or by more vigorous oxidation, acondition Although one of the primary objects of our of drastic oxidation is indicated by changes in invention is to provide a new compound or. comc a a phyfii a 'a t 0f materialposition of matter that is an eificient demulsifier These cha s are usu y di t by a l we d for crude oiiemulsi h of th g q u i iodine value, an increased saponification value,

the saidcommund or composition of matter is usually aneincreased a s y v an in eas d adapted for use in other arts, as hereinafter m specific gravity, and an increased refractive indicated. It also may have additional uses in vari- Thlls. the i e number m y become le ous other fields which have not yet b i than 70, and even as low as about 40. The saponivestigated. flcation value may be about 215 to about 283, and

The composition f mtterherein described. theacetyl value may be about 160 to about 200. par icularly when it is intended t be d as a The viscosity is increased and the drasticallydemulsifier for petroleum emulsions of the wateroxidized product may become very heavy and stiff in-oil type, is obtained by th hydroxya et l at ordinary temperatures. The refractive index tion of a drastically-oxidized dehydr t d m m is also increased. The color of'the drasticallyleic acid compound or the kind hereinafter de- Oxidized material may be a P818 Ye11W i scribed, particularly a drastically-oxidized demay be a deep orange color. If oxidahydrated castor oil. tion' is carried on long enough a product of liver- The expression ricinoleic acid compounds" is like consistency and dark color is obtained. intended to ref r to ricmoleic acid, polyflcmdleic I The same sort-of procedure which is used to acid, and particularly, th glyeerides of ricmoleic oxidize riclnoleic acid compounds which have not acid. sp cifically, th expres ion includes monog been subjected to pyrolytic dehydration, such as ricinolein, diricinolein, ricinoleic acid, etc. Castor ordinary Castor on of commerce may also.

oil of commerce contains approximately 85-90% ployed oxidize dehydrated cast)? O Similar of trh-ioi m and due t its availability and material of the kind herein intended as aprimary low cost, i th preferred raw materiaL raw material. Generally speaking, however, the It is well known that ricinoleic compounds ,followins d fi a should b t in mind: WhlOh hav t b subj t d t pyrolyti Such materials are apt to contain at least a ydration, may beoxidized in various manners. Significanii' ammmt 01f Octfldecadiene -a d- This is usually accomplished by subjecting a 40 or its ester, which is recognized as a powerful ric noleic compound to treatment, such as, blowcata for Promoting x a ion of caster-oil or 8 with a suitable gaseous oxidizing medium, i: e., similar materials, Thus, it is rarely necessary to xygen, ozone, or ozonized air. Such oxidaadd any catalyst to hasten oxidation Furthertionis commonly carried out at ordinary or supermoie, it is rarely. 11806551? to oxidize under Pres; atmospheric pressure (up to about 200 pounds per u aa ush su h p oc u e ay be em oyed.

' square inch) elther moist or dry; and in the pres- It is rarely necessary to use oxygen instead g ence of or absence oi a catalyst, such as lead It rarely n ry to oxidize at a-teim oleate, cobalt linoleate, or manganese oleate, or P ur above 12 C... Thus, notwithstanciloo such as alpha pinene or linseed oil, etc; Care 59 the fact that any of the usual procedures should be taken, however, not to permit temperap oy d for oxidizing castor oil m y be empl y ture rise such that excessive pyrolytic decomposifor oxidizing dehydrated oastor oil, yet, generally tiioxcir'wiiuld' gals; place. bilhwen oxidation any be 7 pe ng, considerably less drastic conditions are 8 o ..a$ y sorous' o g, or ma more re uired. graduali as by exmsm e in mm y q Furthermore, the time element can be s to air. prc as decreased greatly. The same sort or apparatu v and the same sort of procedure is employed as in 'thecase of conventional oxidation of castor oil.

.ISince' dehydrated castor oil is already polymerized to ajjgreater or lesser degree, and perhaps has initial viscosity considerably greater than that of castor.oil ,-it is obvious thatthe final stages of oxidation must be carried out more cautiously, and that excessive oxidation may produce a solid.

or spongy or rubber-like material withoutprevious-indication of the imminent critical stage.

In any event, theflmaterial, prior to oxidation. should be analyzed and oxidation should be con- 4 I 375,681 1 Percent unsaponiflable matter. Generally less than 3% Percentnitrogen-1, 1 1 0.0% Percent s 1 0.0% Percentash 1 Trace Specific gravity at 31 C About 0.9574 .Refractive index at 31 C 1 About 1.495 Color ..1 Straw or light amber ducted until there is a significant change, as indlcatedb'y' increase in viscosity, change in such 'indices as iodine number, hydroxyl number, etc.

all of which is obvious tothose skilled in the'art.

a matter of fact, unless one desires to do so,

there is no need to oxidize such dehydrated castor oil, insofar that various products of this kind are sold commercially and used in other arts which nave no particular connection with the usageherein contemplated.

Castor oil or similar' materials of the kind described have been'dehydrate'd, and such dehydrated materials used for various other purposes, for instance, as substitutes fordrying oils, as plasticizers in the manufacture of resins, as ingre- A specific example of a very desirableoxidized dehydrated castor oil for use in the practice of this inventionand which is available in the open marvket, 1 has approximately the following specific dients entering into the compounding of insulating materials, etc. Generally speaking, the conventional procedure is to subject a quantity of castor oil to destructive disti1lation,-approximately 250-310' C., and generally, 250-285 C.,

The above values or similar values are of assistance in' indicating and characterizing a material 1 of the kind herein contemplated. For instance,

until at least 545% of the original volume has been removed as adistillate. Sometimes the procedure is conducted primarily to recover the-disti'llate, due to its high content of heptaldehyde.

Generally speaking, the lower limts of the mate'- rial distilled oil are approximately 8-10%, and the upper limits, possibly 15-23%. Insome instances, pyrolysis is conducted in presence of an added catalyst, which may permit the reaction, i. e., the degradation or destructive distillation, to take place at lower temperature; and sometimes vacu 'um is employed, or both vacuum and a catalyst.

Such procedure of subjecting a ricinoleic acidcoinpound.. and especially ricinoleic acid or castor oil, to pyrolysis,is so well known that no further elaboration is required. However, for convenience, reference is made to the following patents, which clearly describe the procedure, and insome instances,- point out,a'.t least some of the compli-.

catedchemical changes thattake place; U. S.

Patents NOS. 1,240,565, Harris, Sept. 18, 19 17;

. 1,749,463, Bertsch, Mar. 4, 1930; ,1,799,420, Holton,

-'. 7,1931; 1,886,538, Fanto, Nov.. 8, 1932; l',892,-.- -258, Ufer, Dec. 27, 1932; 2,156,737, Priester,

' May 2,1939; and 2,195,225, Prlester, Mar. 26, 1940;

.and British PatentNo', 306,452, Scheiber,'May 9,

j -As to a comparative evaluation of various dehydratlon catalysts for castor 011, see Masloboino-pzhirovanya Prom. 16v No.-5/6,- 33-8 (1940). The products which-we prefer to use as reactants in. the present instance, are 'blowndehycastor oils-having substantially the following identifyipgcharacteristics within the rangesindicated: Acid number 14.0 mi 25.0 poniflcation number 195 to 240 Iodine n mber.' .1 "10 to 95 number 63.0 to 80.0 iReichert-Meisel'number 5 T 200 and that the 'of60to75. 1

although the entire chemistry of the dehydration of castor' oil is not known, yet obviously, there a must be amarked'reduction in-the. acetyl or hydroxyl value, and simultaneously an increase in the iodine value. Also, such pyrolytic reaction. tends to eliminate the low molal or volatile acids.

Qnoxidatlon of suclnmaterial, the acetyl value or hydroxyl value may stay constant or increase. But, in any event, the iodine value is reduced until it begins to approximate that oi castor oil. or ricinoleic acid prior to dehydration, or somewhat lower. The fact that the acetyl value or hydroxyi value does not increase proportionally withthe drop in the iodine value is, of course, due to eitherv the formation ofether type compounds, or.

'. oxides which do not give ahydroxyl or acetyl value, or else, due to the formation of'ester acids or similar reactions. It is generally desirable that the iodine number of the drastically-oxidized dehydratedcastor'oil be not less than 70, that the saponification value be within the range 195 to acetyl value be within the range The production of hydroxyacetylated drastically oxidized dehydrated castor oil, or a similar type of compound, is comparatively simple and is comparable to the manufacture of acetylated castor oil, except-that hydromaceticacid appears to be more reactive than aceticac'id, and instea'd of using caster oil, oneemploys drastically-0x15 dized dehydrated castor oil as a reactant. Since drastically-oxidized dehydrated castor oil is characterized by the presence of a hydroxyl group or .groups, as indicated by the diydroxylivalue or .number, it is obvious that .esterlfication must take place, and thus the reactant is conducted in such a manner and under-such conditions as'to' promote esteriiication and remove any water formed.

The usual procedures for promotion of esteriflcation'a're well known, and involve one. or more of. the iollowinz: Employment of a, temperature high -"enou gh to eliminate any water formed iorin stance, -180 0.; sometimes the presence of a strong acid, such as. a'benze'ne-sulfonic acid in smallamounts acts as a catalyst; sometimes it is expedient to pass an inert dried. gas through the reacting mixture; at other times esterification may be conducted in the presence of a high'boiling the water vapor and solvent'vapor, is separated by gravity; and the solvent returned to the reacting chamber for further use. I

The selection of suitable amounts oi! reactants in the manufacture ofhydroxyacetylated drastically-oxidized dehydrated castor oil or the like, is, of course, simple. 'One may select a drastically-oxidized dehydrated castor oil corresponding, for example, to the type previously described by analytical values. The hydroxyl or acetyl value or number includes the hydroxyl groups attached to each of thehigh molal acyl radicals present. The chemical changes occurring in the manufacture of drastically-oxidized dehydrated castor oil indicate that the final product is, in essence. a glyceride, or at least, to the extent of a majority percentage. With this in mind, it is apparent that the hydroxyl groups may be distributed more or less uniformly in regard to the three high molal acyl radicals present in such glyceride.

For convenience, in the present instance, one may consider such product as comparable to triricinolein, and as if it were a trihyda'ic alcohol. triricinolein one can obtain monohydroxyacetylated triricinolein, di-hydroxyacetylated triricinolein, and trihydroxyacetylated trirlcinolein. Similarly, based on molar proportions, one can obtain a mono-hydroxyacetylated drasticallyoxidized dehydrated triricinolein, a di-hydroxyacetylated drastically-oxidized dehydrated triricinolein, and a tri'-hydroxyacetylated drastically-.

' moderate excess of hydroxyacetic acid may be employed, over and above the amount indicated by the acetyl number'or value.

Thus, the product particularly contemplated in the present instance, is the compound or compounds obtained by the hydroxyacetylation of drastically-oxidized dehydrated castor oil. For purposes oi convenience, reference will be made to mono-hydroxyacetylated drastically-oxidized From dehydrated castor oil, di-hydroxyacetylated drastically-oxidized dehydrated castor oil, and tri- 'hydroxyacetylated drastically-oxidized dehydrated castor oil. Examination of the reaction indicates that water is'formed and must be removed. Actually, the water formed may not necessarily be removed instantly, and thus, may undergo certain other obvious reactions. Likemately 1 hour.

it is to be noted that such material may be present ,cogenerically, for reasons. indicated.

The lower glycerides are comparable to monoolein or di-olein, and are referred to generally as superglycerinated fats, or more specifically, superglycerinated triricinolein, or s'uperglycerinated castor oil. Inthe presentinstance, the

proper nomenclature would be superglycerinated drastically-oxidized dehydrated castor oil. Actually, if one desired, such products or cdmpounds need not be obtained by hydrolysis, but one could treat one mole of drastically-oxidized dehydrated castor oil with one or two moles of glycerol in the customary manner, so as to cause rearrangement to take place, i. e., so as to obtain'the lower glycerides.

Earlier reference to the compounds herein contemplated, and particularlyfor use as a demulsifier, included the hydroxyacetylated derivatives of drastically-oxidized dehydrated ricinoleic HYDROXYAOETYLATED DRAs'rIcALLY-Oxmrznn I Dnmzmmrsn Casroa 'O'IL Example 1 1,000 pounds 015 drastically-oxidized dehydrated castor oil, comparable in chemical characteristics to the tabular specification appearing previously, is treated with, 37 pounds of concentrated hydroxyacetic acid containing 30% of water. The selected amount is suflicient to combine with onethird of the available hydroxyl radicals, as indicated by the acetyl value or-number. The reaction is conducted at 200-250 C. for approxi- Completeness in reaction is indicated by the'fact that elimination of water practically ceases, decrease in acid value and hydroxyl value of mixture, and elimination of free hydroxyacetic acid. The procedure is conducted in the usual reaction vessel of the kind employed for esteriflcation, and may be constructedoi any material which'is resistant tothe reactants. The amount of'hydroxyacetic acid selected in the present instance is calculated so as l dehydrated castor oil.

wise, for reasons of economy, it may be desirable to use a highly concentrated hydroxyacetic acid instead of the anhydrous material as the selected reactant. In .such instances, the water would readily enter linto hydrolytic. reactions with the drastically-oxidized dehydrated castor oil, and thus, the product or composition which is actually hydroxyacetylated may include the estolides,

HYnnoxyAcnmArnn DxAsncAtLY-Oxrnrzso DIH'YDRATED CAsroa On.

' Example 2 The same procedureis employed as in Example 1, preceding, exceptthat twice the amount of.

HYDROXYACETYLATED DaAsrIcALLY-Oxmmn Dnmrnnarm CASTOR On.

Example 3 The same-procedure is followed as in Example tion'between hydroxyacetic acid and glycerol, but

-1, preceding, except that three times the amount.

1 of hydroxyacetylated castor oil is employed so as to yield substantially .a tri-hydroxyacetylated blown dehydrated castor oill Hrnizoxucnmrrn DalisrrcAtLY-Oxmrzzn m Cssroa on.

Example 4 The same procedure is followed as in Examples 1 to 3, preceding, except that anhydrous hydroxyhydroxyacetylated drastically-oxidized dehy- Previous reference has been made to monodrated castor oil, di-hydroxyacetylated drastically-oxidized dehydrated castor oi-1,---etc.

out that drastically-oxidized dehydratedcastor oil may have an acetyl number or value of 75;

, This value may be considered as being distributed l0. acetic acid is employed and water is removed immediately upon formation. The product so obtained represents hydroxyacetylated blown de-' hydrated castor-oil, or more especially, hydroxyacetylated blown dehydrated triricinolein, in the presence of a .minimum amount of hydroxyacetylated cogeners.

Hrnaoxucxrrmran DaAsrrcArrr-Oxm DIHYDBA'I'ID CASTOR. On.

- Example 5 The same procedure is'followed as in Examples 1 to 4, preceding, but instead or using the stoichiometric amount of hydroxyacetic acid to yield a completely 'hydroxyacetylated product, one emover 3 acyl radicals, or to state it another way, as i being an acetyl value of per acyl group. Thus, the preparation of a monohydroxyacetylated product would involve sufilcient reactant so as to convert one-third of the acetyl value or number, to wit, 25. A di-hydroxyacetylated product would involve'sufllcient reactant to convert two-thirds or the equivalent of an acetyl value 0175, A trihydroxyacetylated product would involve 'sumcient reactant to eliminate the entire acetyl value or '15. i The herein described chemical compounds or,

- products are of distinct value as a break inducer ploys an excess, for instance, a 10-20% excess of hydroxyacetic acid. I

- Nothing that has been said previously is intended to suggest that one cannot use chemically pure or technically pure triricinolein as an initial raw material instead of castor oil. Furthermore,

one may obtain or preparediricinolein, either l pure or of a technical purity, and such material 'may be employed as an initial raw material.

Likwis, pure or technically pure mo'noricinolein; or ricinoleic acid may be employed. For obvious reasons, however, nothing is ordinarily gained by using any initial raw material other than castor oil, andlwe have found castor oil to yield much more eflectlve demulsiflers'than the other materials referred to. Thus, our preference, by far,- is to employ castor oil as the initial raw material.

and to subject it to drastic oxidation and dehy dration.

In view f what has been said, itis obvious that inthe he eto appended claims there cannot be any satisfactory means of characterizing the products as such, or for use as demulsiflers. ex-

cept in terminology, which is related to the method of manufacture.

The expression drastically-oxidized or drastic oxidation," asemployed in the hereto appended claims, refers to gaseous oxidation by means of an oxygen-containing medium. Such expression does not contemplate wet oxidatiqm.

or oxidation by means of permanganate, or other .comparable oxidizing agents.

in the doctor treatment of gasolinejor the like,-

as described in U. S. Patent No. 2,157,223,, to Sutton, dated May 9, 1939.. Other additional uses include application as plasticizers, in plastics,"-

synthetic resins, etc., and particularly in the acetate type, i. e., thecellulose acetate, vinyl acetate, and similar types. a 4

Having thus described our invention. what we claim as new' and desire to secure-by Letters Patent is: 4 1

1. A hydroxyacetylated drastically-oxidized dehydrated ricinoleic acid compound selected 2. A hydroxyacetylated drastically-oxidized dehydrated castor oil.

3. A tri-hydroxyacetylated drastically-oxidized dehydrated castor oil. a I 4. In the manufacture of the compound described in claim 1, the step of hydroxyacetylating a drastically-oxidized dehydrated ricinoleic acid compound selected from the 'class consisting-of drastically-oxidized dehydrated castor oil, drastically-oxidized dehydrated trlricinolein, drasti-,

cally-oxidized dehydrated diricinol ein, drastically-oxidized dehydrated monoricinolein,'dras- It is furthermore understood that hydrox yacete f I ylation can be conducted by means of .the chemical equivalent of hvdroxyacetic acid,as well as the acid itself, for example, the anhydride or acyl chloride.

drated castor oil. I

tically-oxidized dehydrated ricinoleic acid, drastically-oxidized dehydrated polyricinoleic acid, and the estolides of drastically-oxidized .dehy- ELVIN D GHOOTE. BERNHARD' xmsnn. AR'I'I-IUB r wm'rEL. v

It is believed that the meaning of these expressions is perfectly clear. For instance, it has been pointed 

